Trivalent ion overcharging on electrified graphene

Abstract: The structure of the electrical double layer (EDL) formed near graphene in aqueous environments strongly impacts its performance for a plethora of applications, including capacitive deionization. In particular, adsorption and organization of multivalent counterions near the graphene interface can promote nonclassical behaviors of EDL including overcharging followed by co-ion adsorption. In this paper, we characterize the EDL formed near an electrified graphene interface in dilute aqueous $YCl_3$ solution using in situ high resolution x-ray reflectivity (also known as crystal truncation rod (CTR)) and resonant anomalous x-ray reflectivity (RAXR). These interfacial-specific techniques reveal the electron density profiles with molecular-scale resolution. We find that yttrium ions ($Y^{3+}$) readily adsorb to the negatively charged graphene surface to form an extended ion profile. This ion distribution resembles a classical diffuse layer but with a significantly high ion coverage, i.e., 1 $Y^{3+}$ per 11.4 $\pm$ 1.6 A$^2$, compared to the value calculated from the capacitance measured by cyclic voltammetry (1 $Y^{3+}$ per ~240 A$^2$). Such overcharging can be explained by co-adsorption of chloride that effectively screens the excess positive charge. The adsorbed $Y^{3+}$ profile also shows a molecular-scale gap ($\geq$5 A) from the top graphene surfaces, which is attributed to the presence of intervening water molecules between the adsorbents and adsorbates as well as the lack of inner-sphere surface complexation on chemically inert graphene. We also demonstrate controlled adsorption by varying the applied potential and reveal consistent $Y^{3+}$ ion position with respect to the surface and increasing cation coverage with decreasing applied potential.